Condensation product and method of preparing and using same



, Patented July 4, 1944 UNITED STATES PATENT ornca CONDENSATION PRODUCT AND METHOD 013 PREPARING AND USING SAME Eugene Lieber, West New Brighton, Staten Island,

N. Y., assignor to Standard Oil Deveiopmen Company, a corporation of Delaware No Drawing. Application April 20, 1940,

Serial No. 330,697

. 13 Claims.

This invention relates to a novel type of Friedel-Crafts condensation product and tomethods of preparing such products and using them for various purposes, more particularly as pour depressors in waxy lubricating oils.

Heretofore, the chief commercial method of making Friedel-Crai'ts condensation products which could be used as pour depressors in waxy lubricating oils, consisted in reacting a long chain aliphatic chlorinated hydrocarbon such as chloriof high molecular weight should be used, and in,

the British Patent 440,918 where paramnic hydrocarbon material having at least 12 carbon atoms is specified.

Contrary to the above teachings of the prior art, applicant has found that a new type of pour depressant canbe prepared by starting with halogenated paraflinic hydrocarbons having only a short chain, 1. e. not more than 6 carbon atoms, in the Friedel-Crafts condensation with aromatic compounds. Accordingly one object of the invention is to make such condensation products having particular utility as pour depressors in waxy lubricating oils, and otherwise useful as wax modifiers. Another object of this invention is to make such variation in the condensation reaction conditions (as compared to prior art processes) as are necessary to bring about the production of the desired novel condensation products.

One of the big advantages of this invention is that the new type of raw material used, namely, a halogenated paramnic hydrocarbon having not tendency forchlorinated hydrocarbons of sub stantially the same type to be produced.)

Broadly, the invention comprises the production of pour depressants by reacting a halogenated paraflinic hydrocarbon having not more than 6 carbon atoms, with an aromatic compound in the presence of a. Friedel-Crafts condensation product and recovering from the condensation product a fraction which is substantially free from materials removable by fire and steam distillation up to about 600 F.

The halogenated paraflin hydrocarbons to be used are preferably alkvl halides having 1. to 6 carbon atoms and the halogen is preferably chlorine. A particularly suitable material is a. commercially obtainable mixture of amyl chloride; these chlorides contain but 5 carbon atoms and only l chlorine atom per molecule and they can be represented by the formula CsHnCl, although they consist of a mixture of the various isomers of mono-chlorpentane.

As the aromatic compound, a wide variety of materials is available for carrying out the reaction. For example, mono-, dior'other polynuclear carbocyclic compounds, including hydrocarbons such as benzene, naphthalene, anthracene, xylene, fluorene, etc., amines such as more than 6' carbon atoms, is available commercially'in large quantities at relatively low cost and can readily be produced in uniform quality, whereas it is relatively difficult to produce a chlorinated paraffin wax of precisely the desired and uniform properties. (This may be due to the fact that during the chlorination the chlorine molecules may attack the long chain hydrocarbon molecule at a large number of positions along the chain with the result that there will be a substantially greater difference in properties between a molecule having a chlorine atom at one end and a similar molecule having a chlorine atom at the middle of the long chain, wherein properties is not so great and there is more aniline, alpha-naphthylamine, etc., phenols such as phenol itself, alpha-naphthol. cresol, etc., or ethers having the general formula Ar--0-R, where Ar ,is an aromatic hydrocarbon group and R is any organic radical such as an aliphatic, cyclic, or mixed hydrocarbon group, e. 8. Phenetole (phenyl ethyl ether), anisole (phenyl methyl ether), diphenyl ether, etc.; ketones, preferably having the general formula Ar-CO-R, where Ar is an aromatic hydrocarbon group and R is an organic group such as an aliphatic, cyclic or mixed hydrocarbon group, e. g. diphenyl ketone,

dibenzo-phenone, aceto-phenone, beta-naphthyl methyl ketone, dicresyl ketone, dibenzyl ketone, benzyl methyl ketonc. phenyl naphthyl ketone, cyclohexyl phenyl ketone, etc., or other obviously equivalent aromatic compounds.

The catalyst or condensing agent is preferably anhydrousaluminum chloride, although other Friedel-Crafts agents may be used such as the anhydrous halides of iron, zinc, tin, antimony} boron, etc., or mixtures thereof. Usually the amount of catalyst, e. g., aluminum chloride should be between the approximate limits of 5% to 50%, based on the weight of alkyl halide used, although substantially larger quantities can. be used; preferably the amount should be about 10% to 20%.

The reaction is preferably carried out in the presence of a substantially inert solvent or diluent such as a highly refined kerosene or tetrachlorethane, carbon bisulflde, etc.

The reagents are mixed in preferably simple molecular proportions and in general a molecular ratio of aromatic compounds to alkyl halides of 1:1 is preferred, although other ratios may be used, for instance, 1:3, 1:6 and 1:10. The amount of catalyst to be used can vary within wide limits as only a relatively small amount of catalytic quantity is necessary, for instance, as little as 5% or of the weight of the alkyl halide, although if desired, much larger amounts the may be used such as even up to 40 or 50% of weight of the alkyl halide.

In carrying out the condensation reaction, the alkyl halide and aromatic compound may be mixed, together with the solvent it one is used, and then, while the mixture is being agitated, the catalyst is added gradually so that the temperature will not be allowed to rise excessively at any one time. After the addition of the catalyst, the reaction mixture is heated to 200-300 F., or even, in certain instances, up to 500 F., and maintained at the desired maximum temperature for several hours or until substantially all evolution of hydrogen chloride or other hydrogen halide has ceased. The reaction mixture is then cooled and preferably diluted with a further quantity of inert solvent, and finally neutralized or hydrolyzed by any of the known methods familiar to the art of Friedel-Crafts reactions,

for instance, by water, alcohol, dilute aqueous caustic soda and the like. A mixture'of water and alcohol is very convenient. The mixture is then allowed to settle and the aqueous layer containing the catalyst sludge is drawn on and discarded, whereas the organic or upper layer is then distilled with fire and steam to about 600 F. to remove the solvent and low-boiling products. The residue is a poly-alkylated aromatic condensation product which, in some instances, is a blue, green or even brown viscous liquid and in some cases a dark brown resinous or lighter colored sticky or waxy solid. 7

Although it is not desired to limit the invention to any particular theory as to the structure of the product, it is believed that this product is essentially an aromatic nucleus having condensed thereon a suflicient number'of short aliphatic groups to impart pour-depressing properties thereto. For instance, a product believed to be penta-methyl naphthalene has been prepared which, in 2% concentration, reduced the pour point of a waxy lubricating oil from +30 F. to 10 F., and a product believed to be hepta-ethyl naphthalene similarly reduced the pour point to 15 F. The exact number of alkyl or other aliphatic groups having 1 to 6 carbon atoms, required to impart pour-depressing properties to an aromatic nucleus, depends upon the nature 0! the latter, the number of carbon atoms in the aliphatic group and perhaps also on the position of the various groups, although the eflect of position has not yet been determined with certainty.

This product has the property of modifying the crystal structure of waxes such as paraflin wax present when added to compositions containing same. For instance, when about .05-10.0%, preferably 0.2-5.0%, of this wax modifier is added to a waxy lubricating oil such as a Pennsylvania type lubricating oil having a relatively high pour point, the resultant blend will have a substantially lower pour point; in other words, this wax modifier is an effective pour depressor for waxy oil. A small amount of this wax modifier is also useful as a dewaxing aid for removing wax from mineral lubricating oils of undesirably high wax content. In similarly small amounts, this wax modifier may also be incorporated into parafiln wax or compositions containing the same to be used for various purposes such as for coating or impregnating paper, etc., or for making various molded products.

For the sake of illustration but without desiring to limit the invention to the particular materials used, the following tables of experimental data are given:

Tum-1.Aromatic ethers (heated to 200 F. for 3 hrs.)

Solvent Product T t Arom. compd., Gm fi s; Acyi halide, AlOli, Yield, F. pour point 4 es name 0c. gm. gm. gm. per cent added Name Go. Nature Diphenylene oxidc.. Kerosene-- 200 10 do CzHaCli..- 200 10 150 30 Kerosene.. 150 30 o---.--- 150 I 20 02111014-.- 150 10 o..- 150 30 Ker-coma- 150 30 150 30 TABLE 2.Aroma.tic ketones (heated -to 230 F. for 2 /2 hrs.)

Solvent Product T t Arom. compd., G Acyl halide, A101,, Yield, -r. pour point as name gm. gm. gm. per cent added Name 00. Nature 1-.-... Dibenzyl ketone-... 100 168 0511014... 200 15 83 Dk. brown resin 2.4.-- Naphthalene 64 53 Benzoyl O1, o.-- 200 53 4 35 ....d 3-.- Benzene 39 d T. c. e-. 200 60 47 Dark resin 77 63 200 60 127 Dark green resin 77 53 .--.-do Kerosene-- 200 60 72 -.do 50 206 Acetyl Cl, 5 T. c. a-.. 200 111 Dk. bl. vise. liq 250 Acetyl Cl, 62... do. 200 104 96 Dark res 75 156 Acetyl Cl, 39... .do. 200 66 70 Dark br. resin -15 This 3.Aromatic hydrocarbons and misc. (heated to 200 F. for 5 hrs.)

Solvent Product Arom. compd., 1 Ac lhalide A101,, Yield, 7 F. pour point Test name hang; gm. gm. gm. per cent adde Name 00. Nature 1 Benzene 50 50 Kerosene 500 50 39 Dk. green vise. oil 0 -15 2. o-OH dlphenyl 50 50 o 600 50 85 Green brittle solld. 0 3..." Naphthalene 50 60 500 60 73 Dk. brown res. solld 0 4..- Diphenylamine.. 50 50 500 50 37 Dk. visc. oil --10 -25 5 .do .l 50 300 600 50 71 o... 0 6 Phcnanthrene 60 50 500 50 63 do -l0 7"..- Fluorene 50 50 500 50 48 Dk. resin sticky solid 0 8. Dipheuyl 50 50 600 47 Br. resin sticky solid 0 9 Chrysene- 50 50 600 64 Orange waxysolid 0 10. Carbazole 50 300 o. 500 128 Dk. gr. tacky visc. oil. 5 ll Anthraeene 50 34 do. 10 26 Dk. resin solid 20 -30 1 M01. ratio cram/elk. 1181. 1:1.

Table 1 shows the results obtained when the aromatic compound used is an ether such as diphenylene oxide, whereas Table 2 shows the results when using various aromatic ketones and Table 3 aromatic hydrocarbons and amino hydroxy and other derivatives thereof. In almost all of the tests the finished high-boiling condensation products had a pour-depressing p.0- tency such that a 2% addition to a waxy lubricat- 1 Mol. ratio aromJalk. he]. 1:3.

8 Mol. ratio cram/elk. hal. 1:6. 4 Pour point of orig. oil=30 F to 6 carbon atoms, in the presence of a Friedel- Crafts catalyst and an inert solvent, at a teming oil having an original pour point of F.,

reduced the pour point of the blend at least down to 0 and in some instances down to 25 or even 0 F. In all the tests the alkyl'halide used was a liquid composed of a commercially available mixture of am] chlorides.

It is not intended that this invention be limited to any of the specific examples which were given merely for the sake of illustration nor to any theory as to the mechanism of the operation of the invention but only by the appended claims.

Iclaim:

1. A composition comprising a Friedel-Crafts' condensation product of a monomeric aromatic compound and an aliphatic monohalogen substituted hydrocarbon having 1 to 6 carbon atoms, said condensation product being substantially free from materials removable by a fire and steam distillation up to about 600 F., and capable of depressing the pour point of waxy mineral oils when added theretoin small amounts.

2. A Friedel-Crafts condensation product of a monomeric aromatic compound selected from the group consisting of aromatic hydrocarbons and amino, phenolic, ether, ketone and heterocyclic derivatives thereof, and an aliphatic mono-halogen substituted hydrocarbon having 1 to 6 carbon atoms, such condensation products being substantially free from materials removable by a fire and steam distillation up to about 600 F., andcapabl of depressing the pour point of waxy mineral oils 'when added thereto in small amounts.

3. The process which comprises condensing a perature of about 200-300 F. hydrolyzing, and removing residual catalyst, and subjecting the condensation product to distillation with fire and steam up to 600 F. to obtain a substantially nonvolatile residue. v

5. Process according to 'claim 4 carried out by first mixing the aromatic compound and halogenated hydrocarbon with the inert solvent, adding the Friedel-Crafts catalyst gradually, heatin the mixture to a temperature between the approximate limits of 200 and 300 F. and maintaining such temperature until substantially no more hydrogen halide is evolved.

6. Process according to claim 4 in which about V2 to 10 mols of halogenated hydrocarbon are used to 1 mol of aromatic compound.

7. The process which comprises mixing 1 mol of anthracene with about /z to 6 mols of mixed amyl chloride and an inert solvent, adding anhydrous aluminum chloride gradually to the mixture, heating the mass to about 200-300 F., maintaining the temperature thereof until substantially no more hydrogen chloride is evolved, treating the reaction product with a hydrolyzing agent, removing the residual catalyst and subjecting the condensation product to fire and steam distillation up to about 600 F. to obtain a substantially non-volatile residue comprising essentially a polyamylated anthracene.

acyl halide and an aliphatic mono-halogen substituted hydrocarbon, in the presence of an inert solvent and a Friedel-Crafts catalyst, heating the reaction mixture to about 200-300 F., and maintaining such temperature until substantially no more hydrogen halide is evolved, treating the reaction product with a hydrolyzing agent, separating the solvent layer from the catalyst sludge layer, and subjecting the solvent layer to a fire and steam distillation to about 600 F. to obtain a substantially non-volatile residue.

9. A composition comprising a major proportion of a mineral oil and a minor amount of a FriedelCrafts condensation product of a monomeric aromatic compound and an aliphatic monohalogen substituted hydrocarbon having 1 to 6 carbon atoms; said condensation product being substantially free from materials removable by a fire and steam distillation up to about 600 F.

10. A composition comprising a major proportion of a waxy mineral lubricating oil and a minor proportion of a wax-modifying compound comalkyl groups having 1 to 6 carbon atoms, attached thereto, said compound being a condensation.

product or an aliphatic mono-halogen substituted hydrocarbon having 1 to 6 carbon atoms and a monomeric aromatic compound substantially tree from materials removable by a fire and steam distillation up to about 600 F.

11. A lubricant comprising a major proportion of a waxy mineral lubricating oil having a relatively high pour point, and a minor proportion of a pour depressor comprising essentially a Friedel-Crafts condensation product or a monomeric aromatic compound selected from the group consisting oi aromatic hydrocarbons and amino, phenolic, ether. ketone and heterocyclic derivatives thereof, and an aliphatic mono-halogen substituted hydrocarbon having 1 to 6 carbon atoms, said compound being substantially free from materials removable by a fire and steam distillation up to about 600 F.

' prising an aromatic nucleus having at least two 12. A lubricant comprising a major proportion of a waxy mineral lubricating oil having a relatively high pour point and a minor proportion oi a pour depressor comprising essentially a Friedel- Crafts condensation product 01 anthracene and amyl chloride, said condensation product being substantially free from materials removableby a tire and steam distillation up to about 600 F.

13. A lubricant comprising a major proportion of a waxy mineral lubricating oil having a relatively high boiling point, and a minor but pour depressing-amount of a Friedel-Cratts condensation product of a monomeric poly-nuclear aromatic hydrocarbon and a chlorinated paraflln hydrocarbon having the general formula C,Hzn+1Cl, where n is 1-6, said condensation product being substantially free from materials removable by fire and steam distillation up to about 600 F; v

EUGENE LIEBER. 

